Quaternated disazo dyestuffs



United States Patent 3,133,052 QUATERNATED DISAZO DYESTUFFS Ernest Merian, liottmingen, and Bruno .l. R. Nicolaus, Basel, Switzerland, assignors to Sandoz Ltd, Basel, Switzerland, :1 Swiss No Drawing. Filed Dec. 8, 1959, Ser. No. 858,068 Claims priority, application Switzerland .lan. 8, 1959 6 Claims. (Cl. 260-158) This invention relates to new quaternated azo dyestuffs of the general formula X- (R +N=NR N=NR OH) wherein R stands for the radical of a monocyclic or polycyclic hereocyclic diazo component which may be substituted by non-ionic substitutents and which contains at least one quaternated nitrogen atom in the ring,

R; for a phenylene or naphthylene radical which may be substituted by non-ionic substituents,

R OH for the radical of an aromatic hydroxy compound coupled in the orthoor para-position to the hydroxy group, or the radical of an enolizable ketomethylone compound, and

X for an anion equivalent to the dyestulf cation.

The process for the production of the new quaternary azo dyestuffs consists in reacting 1 mole of a water-insoluble disazo compound of the formula R N=NR -N=NR OH wherein R stands for the radical of a monocyclic or polycyclic hererocyclic diazo component which may be substituted by non-ionic substituents and which contains at least one quaternable nitrogen atom in the ring, and wherein R and R possess the aforestated meanings, with at least 1 mole of an alkylating or aralkylating agent.

Examples of suitable diazo components R -NH are the amino derivatives of a thiazole, a benzothiazole, a higher condensed thiazole, a pyrazole, a cinnolme, an imidazole, a triazole, a tetrazole, an oxazole, an oxydiazole, a thiodiazole, a benzimidazole, a naphthimidazole, an indazole, a pyridine, 2-, 3- or 4-rnethylpyridine, 3.4-dimethylpyridine, quinoline, isoquinoline, acridine or benzoxazole which may by substituted by non-ionic groups.

The reaction of the water-insoluble azo dyestuffs with the alkylating or aralkylating agent is effected at high temperatures in an inert solvent or aqueous suspension according to circumstances, the medium being buttered if necessary.

Suitable alkylating or aralkylating agents are e.g. the esters of strong mineral acids and organic sulfonic acids, alkyl chlorides, iodides and bromides, aralkyl halides, di-

alkyl sulfates and benzenesulfonic acid esters which may be further substituted such as the methyl, ethyl, propyl, nbutyl esters of benzenesulfonic acid, 2- or 4-methylbenzenesulfonic acid, 4-chlorobenzenesultonic acid or 4-nitrobenzenesulfonic acid. When the alkyl chlorides or bromides used are gaseous or have a low boiling point, e.g., methyl chloride, methyl bromide, ethyl chloride or ethyl bromide, quaternation is best carried out in pressurized boxylic or sulfonic acids.

formate, acetate, propionate, butyrate, oxalate, lactate, tartrate, citrate, crotonate or acrylate ions, or chloride, bromide, iodide, methylsuifate, ethylsulfate, sulfate, carbonate, phosphate, bisulfate, benzenesulfonate, 4-metl1ylbenzene-and 4-chlorobenzenesulfonate ions.

Also suitable are water-soluble double salt compounds of dyestuii bases with certain inorganic salts such as zinc chloride.

Higher fatty acids which may be substituted by nonionic substituents can be used as anion-yielding compounds; examples are caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid or arachidic acid, and unsaturated higher fatty acids such as oleic acid, elaidic acid, eruric acid, geranic acid, linoleic acid, linolenic acid; also other aromatic or aliphatic car- These acids yield salts which are poorly soluble or insoluble in water but which readily dissolve in acetone and dimethylformamide and are therefore well suited for the coloration of lacquers, e.g., nitrocellulose lacquers, and the dyeing of acrylic fibers in the mass.

When the anions used are phosphotungstic acid, phosphotungstomolybdic acid, silicomolybdic acid, silicotungstic acid, various other inorganic complex acdis or double salts, dyestuffs containing sultonic acid or/ and carboxylic acid groups and free dyestuit acids of metal-complex dyestuffs, e.g., 2:1 metal complexes free from sulfonic and carboxylic acid groups, salts are obtained which are insoluble in water and some of them in organic solvents as well. Very attractive and brilliant scarlet lacquers are obtained with a red acid dyestuif of this type, while a blue acid dyestuif yields a similarly attractive green lacquer.

The new basic dyestuffs are suitable for dyeing and printing polyacrylonitrile fibers containing more than of acrylonitrile, e.g., Orlon (registered trademark) and copolymers of acrylonitrile and 5% vinyl acetate, methyl acrylate or methyl methacrylate. On these materials they possess excellent building-up and levelling properties and give deep shades of good fastness to light, washing, perspiration, sublimation, pleating, pressing, water, sea water and bleaching.

The dyestutts according to the invention and their double salts are best applied from an aqueous, weakly acid suspension or solution, preferably in presence of dispersing agents of non-ionic, anionic or cationic character and at high temperature. The dyestulfs can be applied in closed dyeing machines at high temperature under pressure.

With the dyestuffs of the invention blended fabrics having polyacrylonitrile as one of the components can be successfully dyed, while cotton, wool and viscose rayon are reserved. A number of the dyestuffs are suitable for dyeing polyacrylonitrile in the mass in shades fast to light, washing and perspiration. Those derivatives which possess good solubility in organic solvents can be employed for the mass coloration of oils, lacquers, plastic molding compounds and cellulose acetate fibers. Some of the derivatives obtained by laking dyestufif bases with complex inorganic or organic acids or with acid dyestuffs and which are insoluble in organic solvents are applicable as pigments, e.g., for the mass coloration of polyacrylonitrile fibers in red, violet and blue shades of good allaround fastness.

The new basic dyestuffs have many other uses, e.g., the dyeing of tannin-treated cotton, wool, silk, regenerated cellulose, polyamide fibers and paper in all stages of manufacture. It has been found that mixtures of two in place of dimethyl sulfate one of the following alkylating or aralkylating agents is used: diethyl sulfate, benzene-, 2- or 4-rnethylbenzene-, 2- or 4-chlorobenzenesulfonic acid methyl, ethyl, propyl or butyl esters, methane-,

or more basic dyestuffs can be employed with advantage. 5 ethaneor butanesulfonic acid methyl or ethyl esters, In the examples which follow the parts and percentages methyl, ethyl, propyl or butyl chloride, bromide or iodide, are by weight and the temperatures in degrees Centigrade. benzyl chloride or bromide. When gaseous alkyl halides or those of low boiling point are employed, such as meth- EXAMPLE 1 yl chloride, ethyl chloride, methyl bromide or ethyl bro- 22 Parts Of the diSaZO y fi 0f the formula mide, alkylation is carried out preferably in a pressure OCHE vessel. g A typicalfilyemg method for the dyestuffs of the invention is as fo ows. Hero C 35 parts of the dyestuffs of Example 1 and 65 parts of E dextrin are intimately ground. I part of the preparation obtained is suspended in 3000 parts of water at room temare finely ground and dissolved in 1000 parts of boiling perature and 5 parts of acetic acid added to acidify the chlorobenzene, 7 parts of dimethyl sulfate are added dropbath. 100 parts of a scoured fabric of polyacrylonitrile wise to the yellow solution at 100 with thorough stirfiber are entered at 50, the dyebath brought to the boil ring. The solution changes color to blue fairly quickly in 30 minutes and dyeing continued for 1 hour at the and the quaternated dyestuff is precipitated in the form boil. The dyed fabric is then rinsed, soaped for 20 minof hard crystals and on completion of alkylation, which Utes in a boiling bath containing 1 gram P liter of a can be observed from the change of color, it is filtered Orr non-ionic detergent, rinsed and dried. The fabric is dyed and dried. The dyestulf formed is sufficiently pure for in a p levfil blue Shade which has good fastness to practical purposes; it dissolves in sulfuric acid with a light, Washing, Water, milling, P P Sea Water, yellow and in water with a blue coloration and dyes pleating and heat Settingpolyacrylonitrile fibers from aqueous solution in reddish Further Valuable basic dyestuffs which can be Pmducfid blue shades of excellent fastness to light, washing, peraccording to the details given in Examplfi 1 are described spiration, sublimation, pleating, water, sea water and in the following table; they have the formula pressing. Possessing outstandingly good building-up propg erties, it is especially valuable for the production of heavy i shades while its good level dyeing properties are evident q- A H even in shades of light depth.

Similar quaternated disazo dyestuffs are obtained when L 2 Shade of dye- No. R; :c z Ra-OH ing on polyacrylonitrile fibers 2. N-methyl-fiunethoxybeuzothiazolyl-Z- H CH3 H 4'-hydroxypheuyl do OCH3 N -ethyl-6-methoxybenzothiazolyl-2- 0 CH -benzyl-fi-nlethoxybenzothiazolyl-2- 0 CH: 28. N-methylbenzothiazolyl-2- 0 CH; 29. N-methyl-fi-ethoxybenzothiazolyl-2- OCH; 29. N-methyl-G-ethoxybenzothiazolyl-2- O CH; 80. N-Inethyl-G-Inethylbenzothiazolyl-Z- 0 CH5 31. N-methylthia zolyl-2- 0 CH3 32. N-ethylthiazolyl- O CH; 33. N-methylpyridyl-Z OCH; 34. N-methylquin01yl-2- O CH; 35. N-methyl-fi-meth ylthiaz0ly1-2- 0 CH3 36. N-methyltrlazolyl-Z- 00113 37. N-methylbeuzimidazolyl-2- O CH 3 38. N -methyl-fi-methylbenzoxazoly 0 CH3 39. N-methyM-Inethoxybenzoeazoly 0 CH 40. N-methyl-Z-methylpyridyHi 0 CH3 41. N-meth yl-dmethylpyridyl 0 CH 42. N -methyl-isoquinolyl- OCH; 43. N -methy1-6-methox yb enzthi 0 CH 44 N-ethyl-fi-methoxy-beuzothiazolyl-Z OCH:

45. N-methyl-thiazolyl-Z 0 CH3 46. N-methyl-isoquinoly1-3 OCHa blue. H 2-meth vI-4-hydroxyphenyl Do. H 2'-hydroxy-Sunethylphenyl- Do. H 2'-hydroxy-5'-chlorophenyl.. Do. H 3'-acetylamino-4-hydroxypheny Do. H 2-acetylamino-4-hydroxypl1enyl. D0. H 2-hydroxy-5acetylaminophenyl Do. H l-hydroiw-uaphthyl Blue. H 2 -hydroxy-naphthyl D H Phenylpyrazolonyl Reddisll blue. H (PhonylcarbamyD-(acetyl)-methyl Do. H Methylpyrazolonyl Do. H 4-hydroxyphenyl Do. H Do. Do. D0. D0. D0. Violet.

Do. Red-violet Do. Blutitsh v10 Red-violet. Do. Blue-violet. Do. Red-violet. Do. Do. Blue.

Reddish blue.

Do. Red-vlolet.

Shade of dye N0. R1 1 y z R3-OH ing on polyacrylonitrlle fibers 47. N-methyl-acridyl-5 Red-violet. 48. N-methy1-6-methoxy-benzothiazolyl-2. Blue. 49. do Reddish blue. 50. do H Br 51. -..d H CHaOO-NH--- H 52. do H CzH-CONH H 53. N-methyl-Gethyl-benzothiazolyl-2 OCH; OCH: H

54. N-methyl-fi-isopropyl-benzothiazolyl-2 00H; OGHa H 55. N-methyl-fi-tert.butyl-benzothiazolyl-Z. OOH; OCH-4 H 56. N-methyl-fi-phenyl-benzothiazolyl-2 OCH; CH: H

57. N-methyl-6-(4-methyl)-phenoxy- OCHQ CH3 H benz0thiaz01y1-2. 58. N-methy1-6-(4-chloro)-phenoxy- OCHa OH; H

benzothiazolyl-Z. 59. N-methyl-fi-phenoxy-benzothiazolyl-2 H 60. N-methyl-6-ehloro-benzothiazolyl-2 H 61. N methyl-fi-fluoro-benzothiazolyl-2- H 62. N-methyl-G-bromo-benzothiazolyl-Z H 63. N-methyl-6-tri-fluoromethyl-benzothiazolyl-2 OCH H 64. N-methyl-fi-benzyl-benzothiazolyl-2 OCH; H

65. N-methyl-6-benzylow-benzothiazolyl-Z OCH; H 0 Do. 66. N ethyll.6,11imethyl-benzothiazolyl-Z. 0011 H 2-methyl-4-hydroxyphenyl D0. 67. N-methyl-4.7,dimethyl-benzothiazolyl-2 OCH; H 3-methy1-4-hydroxyphenyl Do. 68. N-henzyl-G-methylthio-benzothiazolyl-2 OCHa H 4-hydroxyphenyl D0. 69. Nonethyl-fi-phenylthio-benzothiazolyl-2 OCHa H d0 Do. 70. N%1}:]u ethl-16-2(4-methyl)-phenylthlobenz0- OOHa H 4-hydroxy-naphtyl Blue.

iazo y 71. N-methyloxazolyl-2 OCH3 H 4-hydroxyphenyl Violet.

72. N-ethyl-G-methoxybenzothlazolyl2 O-CzHs 11+: d0 Blue.

CH2CH2CH2CH2. 73. do H '"CHQOHZCHQOH2 D0. 74. do OCHa CHaOHgOH2OH2---- D0. 75. d0 001E; GH=OHOH=CH Do.

In the above table anion stands for Cl, Br, 1-, HSO4 H2PO4'", /2SO ZnCl CH SO C H SO oleate, elaidinate, erucate, linoleate or linolenate ion, in

which case the dyestufi's are less soluble in Water, but are soluble in organic solvents, e.g., acetone, methylene chloride or dimethylformamide, and are thus suitable for dyeing secondary cellulose acetate and triacetate and polyacrylonitrile in the mass and polyacrylonitrile fibers from aqueous dispersion. Finally, anioncan also be a phosphotungstate, phosphomolybdate, phosphot-ungstomolyb-- date, silicomolybdate or silicotungstate ion; the dyestuffs formed with these are insoluble in water and organic solvents and are valuable pigments.

Dyeing Example A In a high temperature dyeing machine a suspension is prepared with 1 part of the dyeing preparation which is prepared according to Example 1 and contains 35% of the dyestuif of the formula Nae-0- in 3000 parts of water at room temperature, 5 parts of acetic acid and 5 parts of Glaubers salt. parts of yarn of polyacrylonitrile staple fiber are immersed in this liquor at 50, the machine closed and theinside temperature increased to Dyeing is continued at this temperature under pressure for 30 minutes. A deep, level blue shade of excellent all-round fastness is obtained.

Dyeing Example B 1 part of the dyeing preparation produced according to Example 1 with the dyestuif of the formula HC-N m": inens-O [cm-s04 "3, 138,052 7 8 Dyeing Example C 1 part of the dyeing preparation produced according to Example 1 with the dyestuii of the formula i 1 CH3 7 r c H s0 C:H6 O /CNNO--l\T N V: HI 2 I 4] V CHa' V is suspended in 3000 parts of water at room temperature E l 45 with the addition of parts of acetic acid. 200 parts" 9 CH3 of a blended fabric composed'of 60% polyacrylonitrile 003 fiber and cotton are entered in the dyebath at 1 fi and dyed for 30 minutes at 125 under presure. A deep, 5 Ho C-N=N -N=NOH [Anion]- level blue shade is obtained on the polyacrylonitrile fiber while the cotton component is reserved. 00H,

Dyeing Example D V Having thus disclosed the invention what we claim is:

2O l 30 parts of the dyeing preparation produced accord- 1 Quaternated dlsaze dyes of the fcrmu a ing to Example 1 with the dyestufi of the formula V (R +N=NR N=NR OH) X- Q CH l 0 CH3 is suspended in hot water with 50 parts of thiodiglycol 30 h r in l 0 CH:

and 10 parts of acetic acid. A gum tragacanth R is a member selected from the group consisting thickening is added to give 1000 parts of a printing paste of N-(lower)-alkylthiazolyl, N-(lower)-alkyloxazolyl, which is applied to a fabric of polyacrylonitrile fiber and N-(lower)-alkylquinolyl, N-(lower) -alkylisoquinolyl, steamed for 30 minutes in a star steamer or, alternatively, N.(1 1k 1 1 1, 1 1k 1 1 in a pressure steamer at 7 lbs. per sq. in. The level blue 35 (lower)-alkylbenzimidazoly1 and N-(lower)-a1ky1 print obtained has very good fastness to light and rubbing. benzothiazolyl, 6-methylbenzothiazolyl, G-ethylbenzo- Formulae of representative dyestufis of the forego ng thiazolyl, 6-methoxybenzothiazolyl, 6-ethoxybenzoexamples as as follows. thiazolyl, 6-phenylbenzothiazolyl, 6-phenoxybenz0- Example 1: thiazolyl, fi-chlorobenzothiazolyl, 6-bromobenzothi- 63 CHI Ili 10m /O--N=NN=NC OH [Anioni S l CH3 Example 6:

pom /CN=NN=N--OH [Anion]- S 0011; Example 26:

l ?UHZ ll I CH: 1.

Example 31: V azolyl, 6 fiuorobenzothiazolyl, 6 trifluoromethyl- CH3 65 benzothiazolyl, 6-rnethy1phenoxybenzothiazolyl, 6- ?CH; chlorophenoxybenzothiazolyl, 6-benzylbenzothiazol- H yl, 6-benzyloxybenzothiazolyl, 6-methylthiobenzothi- HC CN=N N=N-O0 EAniorflazolyl, 6-phenylthiobenzothiazolyl and G-methylphenylthiobenzothiazolyl; 4,6-dimethylbenzothiazolyl; 4,

C 3 7-dimethylbenzothiazolyl; N-methyl-S-methylthiazol- Example 44: yl; 2 methylpyridyl; 3 methylpyridyl; 6 methyl- O O C N=\I N=N O H [Anion]- Ha0 0 \s/ l 16 benzoxazolyl; G-methoxybenzoxazolyl, wherein lower R OI-I is a member selected from the group consistalkyl has 1 to 2 carbons, said R containing at least ing of hydroxy-phenyl, hydroxy-lower alkyl-phenyl, one quaternized nitrogen atom in the ring, hydroxy-lower alkanoylamino-phenyl, hydroxynaph- R is a member selected from the group consisting of thyl, methylpyrazolonyl, phenylpyrazolonyl and phenylene, lower alkyl-phenylene, lower dialkyl- 5 (phenylcarbamyl)-(acetyl)-methyl phenylene, lower dialkoxy-phenylene, lower alkoxyand X'- is an anion which carries the same number of phenylene, lower alkyl lower alkoxy phenylene, charges as the cation in the dyestuff. chlorophenylene, bromo-phenylene, lower alkanoyl- 2. The quaternated azo dyestuff of the formula Q CH3 I OCH: H I N H H S/o-N-N I -N- -0 [o -0-8031 aminophenylene, naphthylene, lower alkoxy-naph- 3. The quaternated azo dyestufi of the formula G3 CH3 ()OH3 H304) /ON=N N=N-C -0H 0113-0403]- s ()CHa thylene, lower alkoxy-S,6,7,8-tetrahydronaphthylene, 4. The quaternated azo dyestuff of the formula 6B oaHb 011 ll /ON=NN=N -OH [C Hr-OS0s] the phenylene and naphthylene radical being linked 5. The quaternated azo dyestufl of the formula l; oon, ll /CN=N- N= -OH [C2H5-0-S081" S I OC a g to the -N=N-bridges in the positions 1 and 4, 6. The quaternated azo dyestuff of the formula GB CH: 2

| 0011;, Hill-ll? I HO O-N= N=N -OH [CH3OSO3] OOHa References Cited in the file of this patent UNITED STATES PATENTS v 2,216,446 McNally et a1. Oct. 1, 1940 2,359,862 Linch Oct. 10, 1944 2,771,466 Towne et a1. Nov. 20, 1956 2,852,504 Towne et al. Sept. 16, 1958 2,864,812 Bossard et al. Dec. 16, 1958 2,893,816 Tsang et al. July 7, 1959 2,913,303 Baumann et al. Nov. 17, 1959 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3, 133,052 May 12, 1964 Ernest Merian et a1,

corrected below.

Column 1, line 15, for "hereocyclic" read heterocyclic line 31, for "hererocyclic" read heterocyclic column 2, line 26, for "acdls" read acids column 3, lines 11 to 15, for the left-hand end of the formula reading:

HC -O= read CH -O columns 3 and 4, in the table, item 39, under the heading "R1", for "N=methyl6-=methoxybenzocazolyl-2" read Nmethyl 6-methoxybenzoxazolyl-2 column 5, the last formula, for the left-hand d of the formula reading:

N C-O- read H 3 columns 5 and o, in the table, item 70, under the heading "R3 OH" for "4 hydroxy naphtyl" read 4 -=hydroxy-naphthyl column 7, line 38, for "as", first occurrence, read are Signed and sealed this 1st day of December 1964.

(SEAL) Attest:

ERNEST W SWIDRR" EDWARD J, BRENNER Attesting Officer Commissioner of Patents 

1. QUATERNATED DISAZO DYES OF THE FORMULA 